Carboxylate of certain polyoxyalkylene amines

ABSTRACT

A process for preparing carboxylates of polyoxyalkylene siloxanes and -amines, alkylpolyoxyalkylenes, polyoxyalkylene block polymers, alkylamidepolyoxyalkylenes and alkylpolyglucosides comprising subjecting a primary hydroxyl group-containing polyoxyalkylene compound or alkylpolyglucoside to mild oxidiation. The invention also relates to the novel polyoxyalkylene amine and alkylamidepolyoxyalkylene carboxylates prepared by the process.

The present invention relates to an improved process for preparingcarboxylates of polyoxyalkylene siloxanes and -amines,alkylpolyoxyalkylenes, polyoxyalkylene block polymers,alkylamidepolyoxyalkylenes and alkylpolyglucosides comprising subjectinga primary hydroxyl group-containing polyoxyalkylene siloxane or amine,alkylpolyoxyalkylene, polyoxyalkylene block polymer,alkylamidepolyoxyalkylene or alkylpolyglucoside to mild oxidation. Theinvention also relates to certain of the carboxylates prepared by theimproved process as novel compounds.

BACKGROUND OF THE INVENTION

Over the last 50 years, numerous polyoxyalkylene containing surfactantsand specialty chemicals have been developed for commercial application(see for example Shick, M. J., Nonionic Surfactants, 1967, MarcelDekker). These materials, in general, have broad utility as emulsifiers,dispersants, lubricants, detergents, antistats, solubilizers, orthickeners in such industries as cosmetic/personal care, householdproducts, textile, paper, I & I, coatings, and resource recovery.

More specifically, silicone containing surfactants are taking on greaterimportance in the cosmetic industry. The major class of these compoundsis made up of a polydimethylsiloxane backbone to which polyethers havebeen grafted through a hydrosilation reaction. The other class is madeup of an ABA block copolymer of polyoxyalkylene (A) andpolydimethylsiloxane (B).

polyoxyalkylene amines are of great importance in the emulsionpolymerization industry and in fiber-related industries where staticcontrol is important. Their polyoxyalkylene branches are composed ofethylene oxide polymers or block copolymers of propylene oxide andethylene oxide.

Moreover, alkylpolyoxyalkylenes, polyoxyalkylene block polymers,alkylamidepolyoxyalkylenes and alkylpolyglucosides are of greatimportance in the detergent industry.

Potentially, all of the above mentioned compounds could be converted tothe corresponding carboxylated derivatives. However, only the alkyl- andarylpolyoxyalkylene carboxylates have been commercialized (via thewilliamson ether synthesis). These products have enjoyed relativesuccess in such areas as cosmetic/personal care, household products,agricultural formulations, and the like. Accordingly, in view of theirapparent usefulness in a variety of applications, a number of researchendeavors have been directed to developing a simple, yet selectiveprocess for preparing carboxylates of polyoxyalkylene siloxanes and-amines, alkylpolyoxyalkylenes, polyoxyalkylene block polymers,alkylamidepolyoxyalkylenes and alkylpolyglucosides, without appreciablesuccess.

Although many suitable processes are known for preparing thecorresponding carboxylates of these materials, none are free of certaindisadvantages which make them rather impractical from a commercialstandpoint. For example, although polyoxyalkylene amine carboxylates maybe prepared by the Williamson synthesis, it has been found that thisreaction indiscriminately leads to both N and O carboxymethylation whichresults in the undesired quaternization of nitrogen atoms. In addition,the carboxylation of alkylpolyglucosides by the oxidation of primaryalcohol sites over platinum catalysts with oxygen as the oxidizer hasbeen thus far commercially unattractive due to economics. Furthermore,no one process has proven to be broadly applicable to all classes ofthese polyoxyalkylene adducts.

DESCRIPTION OF THE PRIOR ART

J. Org. Chem., Vol. 52, pgs. 2559-2562 (1987) discloses a two-phase(water/solvent) process for oxidizing primary alcohols to aldehydes orcarboxylic acids using oxoammonium salts. In addition to the fact thatthis process employs a phase-transfer catalyst, the use of a solvent,viz., methylene chloride, presents problems from a productionstandpoint.

U.S. Pat. No. 4,658,049 discloses certain carboxyl-group containingsiloxane compounds exhibiting superior heat stability, which compoundsare useful as emulsifying agents and surface modifiers for inorganicmaterials. The final products are prepared by subjecting a particularester compound and a particular siloxane compound to hydrosilylation,and subjecting the resultant ester to hydrolysis.

U.S. Pat. No. 3,560,544 discloses certain triorganosiloxy endblockedpolyoxyalkylene siloxane polymers which are useful as wetting agents,detergents and emulsifying agents. The final products are prepared byadding a particular organosilicon compound to any cyclic anhydride of analiphatic carboxylic acid, heating the admixture and recovering thedesired end product.

Although each of the above references discloses a suitable process forpreparing the desired end products, there still exists a dire need for asimple, yet selective process for preparing carboxylates ofpolyoxyalkylene siloxanes and -amines, alkylpolyoxyalkylenes,polyoxyalkylene block polymers, alkylamidepolyoxyalkylenes andalkylpolyglucosides. To this end, the present invention is directed toan improved process for preparing said carboxylates which is quiteattractive from a commercial standpoint.

OBJECTS OF THE INVENTION

It is an object of the instant invention to provide an improved processfor preparing carboxylates of polyoxyalkylene siloxanes and -amines,alkylpolyoxyalkylenes, polyoxyalkylene block polymers,alkylamidepolyoxyalkylenes and alkylpolyglucosides.

It is another object of the instant invention to provide an improvedprocess for preparing carboxylates of polyoxyalkylene siloxanes and-amines, alkylpolyoxyalkylenes, polyoxyalkylene block polymers,alkylamidepolyoxyalkylenes and alkylpolyglucosides which is simple, yetselective.

It is yet another object of the instant invention to provide an improvedprocess for preparing carboxylates of polyoxyalkylene siloxanes and-amines, alkylpolyoxyalkylenes, polyoxyalkylene block polymers,alkylamidepolyoxyalkylenes and alkylpolyglucosides which is simple, yetselective, practical and economical and thereby quite attractive from acommercial standpoint.

DESCRIPTION OF THE INVENTION

The attainment of the above objects is made possible by the instantinvention which involves the mild oxidation of polyoxyalkylene siloxanesand -amines, alkylpolyoxyalkylenes, polyoxyalkylene block polymers,alkylamidepolyoxyalkylenes and alkylpolyglucosides containing primaryhydroxyl groups to the corresponding carboxylates. More particularly,the instant process involves reacting one mole of a primary hydroxylgroup-containing polyoxyalkylene siloxane or -amine,alkylpolyoxyalkylene, polyoxyalkylene block polymer,alkylamidepolyoxyalkylene or alkylpolyglucoside with at least anequimolar amount of either an inorganic or organic halo-containingoxidizing agent in the presence of a weak base and a catalytic amount ofa hindered nitroxide to produce the corresponding carboxylates.

Suitable polyoxyalkylene siloxane carboxylates which may be prepared bythe process of the instant invention include the compounds of formulaIA: ##STR1## where each R is C₁ -C₂₀ alkyl;

each R¹ is C₁ -C₂₀ alkyl, aryl or benzyl;

each m is 0 or an integer 1 to 100;

n is 0 or an integer 1 to 1000; and

each p is an integer 1 to 100.

In the above formula, preferred compounds are those where each R is C₃-C₁₀ alkyl, each R¹ is C₁ -C₆ alkyl or benzyl, each m is 1-10, and n is0 or an integer 1 to 30. The more preferred compounds of the aboveformula are those where each R is C₃ -C₆ alkyl, each R¹ is C₁ -C₄ alkyl,each m is 0, or an integer 1 or 2, and n is an integer 1 to 8.

Other suitable polyoxyalkylene siloxane carboxylates which may beprepared by the process of the instant invention are the compounds offormula IB: ##STR2## where R, each R' and m are as defined above withregard to the compounds of formula IA;

p' is an integer 1 to 200;

each A' has the same significance as

R' defined above or is a group

    R--O--(PO).sub.m --(EO).sub.p'--CH.sub.2 COONa,

where R, m and p' are as defined above; and

x+y is 0 or an integer 1 to 1000.

Of the compounds of formula IB, preferred are the compounds where R isC₃ -C₁₀ alkyl, each R is C₁ -C₆ alkyl or benzyl, m is 1 to 10, p is 1 to150, each A is C₁ -C₆ alkyl, and x+y is 0 or an integer 1 to 600. Themore preferred compounds of formula IB are those where R is C₃ -C₆alkyl, each R is C₁ -C₄ alkyl, m is 0 or an integer 1 or 2, p is 1 to100; each A is C₁ -C₄ alkyl, and x+y is an integer 10 to 300.

Suitable polyoxyalkylene amine carboxylates which may be prepared by theprocess of the instant invention include the compounds of formula IIA:##STR3## where each m is 0 or an integer 1 to 50;

n is O or an integer 1 to 10; and

each p is 0 or an integer 1 to 100.

Of the compounds of formula IIA, preferred compounds are those whereeach m is 0 or an integer 1 to 30, n is an integer 2 to 6 and each p is0 or an integer 1 to 80. The more preferred compounds of formula IIA arethose where each m is an integer 1 to 25, n is an integer 2 to 4 andeach p is an integer 1 to 60.

Other suitable polyoxyalkylene amine carboxylates which may be preparedby the process of the instant invention are the compounds of formulaIIB: ##STR4## where each m is 0 or an integer 1 to 30;

n is 0 or an integer 1 to 10;

each p is an integer 3 to 30; and

x is an integer 5 to 24.

Of the compounds of formula IIB, preferred compounds are those whereeach m is 0 or an integer 1 to 10, n is 0 or an integer 1 to 6, each pis an integer 3 to 10, and x is an integer 10 to 20. The more preferredcompounds of formula IIB are those where each m is 0 or the sum of them's is an integer 15 to 25, n is 0 or an integer 1 or 2, the sum of thep's is an integer 10 to 20, and x is an integer 12 to 18.

Still other suitable polyoxyalkylene amine carboxylates which may beprepared by the process of the instant invention are the compounds offormula IIC: ##STR5## where each m is 0 or an integer 1 to 10;

each p is an integer 3 to 40; and

x is an integer 6 to 24.

Of the compounds of formula IIC, preferred compounds are those whereeach m is 0 or an integer 1 to 10, each p is an integer 3 to 20, and xis an integer 6 to 18. The more preferred compounds of formula IIC arethose where each m is 0 or an integer 1 or 2, the sum of the p's is aninteger 8 to 20, and x is an integer 12 to 18.

Yet still other suitable polyoxyalkylene amine carboxylates which may beprepared by the process of the instant invention are the compounds offormula IID: ##STR6## where each m is 0 or an integer 1 to 20;

each p is an integer 3 to 40; and

x is an integer 6 to 20.

Of the compounds of formula IID, preferred compounds are those whereeach m is 0 or an integer 1 to 10, each p is an integer 3 to 20, and xis an integer 10 to 18. The more preferred compounds of formula IID arethose where each m is 0 or an integer 1 or 2, each p is an integer 4 to10, and x is an integer 10 to 14.

Further suitable polyoxyalkylene amine carboxylates which may beprepared by the process of the instant invention are the compounds offormula IIE: ##STR7## where each m is O or an integer 1 to 40;

each p is an integer 3 to 20;

x is an integer 6 to 20; and

X.sup.⊖ is an anion.

Of the compounds of formula IIE, preferred compounds are those whereeach m is 0 or an integer 1 to 20, each p is an integer 3 to 10, x is aninteger 10 to 18, and X.sup.⊖ is a halide, C₁₋₃ alkylsulfate orphosphate anion. The more preferred compounds of formula IIE are thosewhere each m is 0, the sum of the p's is 10, x is an integer 16 to 18and X.sup.⊖ is a phosphate anion.

Still further suitable polyoxyalkylene amine carboxylates which may beprepared by the process of the instant invention are the compounds offormula IIF: ##STR8## where R is methyl, ethyl or benzyl;

each m is 0 or an integer 1 to 40;

each p is an integer 3 to 20;

x is an integer 6 to 20; and

X.sup.⊖ is an anion.

Of the compounds of formula IIF, preferred compounds are those where Ris methyl or ethyl, each m is 0 or an integer 1 to 10, each p is aninteger 3 to 10, x is an integer 10 to 18 and X.sup.⊖ is a halide, C₁₋₃alkylsulfate or phosphate anion. The more preferred compounds of formulaIIF are those where R is methyl, each m is 0, the sum of the p's is 13,x is an integer 12 to 14 and X.sup.⊖ is a chloride anion.

Suitable alkylpolyoxyalkylene carboxylates which may be prepared by theprocess of the instant invention are the compounds of formula III:##STR9## where R is straight or branched chain C₄ -C₂₂ alkyl, alkenyl oralkylphenyl, or a mixture thereof;

m is 0 or an integer 1 to 50;

n is an integer 1 to 50; and

X.sup.⊖ is hydrogen or an alkali metal cation.

In the above formula, preferred compounds are those where R is straightor branched chain C₄ -C₁₈ alkyl, alkenyl or alkylphenyl, or a mixturethereof, m is O or an integer 1 to 20, n is an integer 1 to 20, andX.sup.⊕ is hydrogen, sodium, potassium or lithium. The more preferredcompounds of the above formula are those where R is straight or branchedchain C₁₀ -C₁₈ alkyl, alkenyl or alkylphenyl, or a mixture thereof, m isO or an integer 1 to 10, n is an integer 1 to 10, and X.sup.⊕ ishydrogen, sodium or lithium.

Suitable polyoxyalkylene block polymer carboxylates which may beprepared by the process of the instant invention are the compounds offormula IV: ##STR10## where m+p is an integer 1 to 400;

n is O or an integer 1 to 200; and

each X.sup.⊕ is hydrogen or an alkali metal cation.

In the above formula, preferred compounds are those where m+p is aninteger 1 to 200, n is an integer 2 to 100, and each X.sup.⊕ ishydrogen, sodium or lithium. The more preferred compounds of the aboveformula are those where m+p in an integer 2 to 10, n is an integer 10 to30, and each X.sup.⊕ is hydrogen or sodium.

Suitable alkylamidepolyoxyalkylene carboxylates which may be prepared bythe process of the instant invention are the compounds of formula V:##STR11## where R is straight or branched chain C₄ -C₃₀ alkyl oralkenyl, or a mixture thereof;

R₁ is H or a moiety ##STR12## m is O or an integer 1 to 50; n is aninteger 1 to 50; and

X.sup.⊕ is hydrogen or an alkali metal cation.

In the above formula, preferred compounds are those where R is straightor branched chain C₄ -C₁₈ alkyl or alkenyl, or a mixture thereof, R₁ ishydrogen or a moiety ##STR13## m is O or an integer 1 to 10, n is aninteger 1 to 20, and X.sup.⊕ is hydrogen, sodium or lithium. The morepreferred compounds of the above formula are those where R is straightor branched chain C₁₀ -C₁₄ alkyl or alkenyl, or a mixture thereof, R₁ isa moiety ##STR14## the sum of the m's is 0 or an integer 1 or 2, the sumof the n's is an integer 4 to 10, and X.sup.⊕ is hydrogen or sodium.

Suitable alkylpolyglucoside carboxylates which may be prepared by theprocess of the instant invention include the compounds of formula VIA:##STR15## where R is n-C₁ -C₂₅ alkyl; and

x is O or an integer 1 to 100.

Of the compounds of formula VIA, preferred compounds are those where Ris n-C₁ -C₁₄ alkyl, and x is O or an integer 1 to 30. The more preferredcompounds of formula VIA are those where R is n-C₁ -C₈ alkyl, and x is Oor an integer 1 to 15.

Other suitable alkylpolyglucoside carboxylates which may be prepared bythe process of the instant invention are the compounds of formula VIB:##STR16## where R is n-C₁ -C₂₅ alkyl; and

x is O to 100.

Of the compounds of formula VIB, preferred compounds are those where Ris n-C₄ -C₁₆ alkyl, and x is 0 to 30. The more preferred compounds offormula VIB are those where R is n-C₁₀ -C₁₃ -alkyl, and x is 0 to 15.

In accordance with the process of the instant invention, theabove-depicted carboxylates are prepared by reacting a primary hydroxylgroup-containing polyoxyalkylene compound or alkylpolyglucoside, e.g., apolyoxyalkylene siloxane of the formula ##STR17## where each R, each R',each m, n and each p are as defined above regarding the compounds offormula IA, or a polyoxyalkylene amine of the formula ##STR18## whereeach m, n and each p are as defined above regarding the compounds offormula IIA, with from 1 to 10 moles of an inorganic or organichalo-containing oxidizing agent in the presence of a weak base and acatalytic amount of a hindered nitroxide compound to produce the desiredcarboxylates.

As to the oxidizing agent, any inorganic or organic halo-containingoxidizing agent can be utilized in the process of the instant invention-Preferred inorganic halo-containing oxidizing agents are the alkalimetal and alkaline earth metal hypochlorites and hypobromites, alkalimetal bromites and chlorine gas, whereas preferred organichalo-containing oxidizing agents are trichloroisocyanuric acid,tribromoisocyanuric acid, N-chlorinated and N-brominated succinimidesand chlorinated nylon 66. More preferred inorganic halo-containingoxidizing agents are the alkali metal hypochlorites and bromites andchlorine gas, whereas more preferred organic halo-containing oxidizingagents are trichloroisocyanuric acid and chlorinated nylon 66. Theoxidizing agent is preferably employed in an amount of from 2 to 6 molarequivalents of the primary hydroxyl group-containing polyoxyalkylenecompound or alkylpolyglucoside, more preferably in an amount of from 3to 4 molar equivalents of the primary hydroxyl group-containingpolyoxyalkylene compound or alkylpolyglucoside.

Although any weak base may be employed in the process of the instantinvention, the alkali metal bicarbonates are preferred, more preferablysodium and potassium bicarbonate. The weak base is added in an amountsufficient to adjust the pH of the reaction mixture to between 8.0 and9.0, preferably between 8.5 and 9.0.

With regard to the catalyst, the hindered nitroxide compound (alsoreferred to in the literature as a hinderediminoxyl or N-oxyl compound)is employed in an amount of from 0.001 to 1 molar equivalents of theprimary hydroxyl group-containing polyoxyalkylene compound oralkylpolyglucoside. Preferably, the catalyst is employed in an amount offrom 0.01 to 0.10, more preferably 0.02 to 0.04, molar equivalents ofthe primary hydroxyl group-containing polyoxyalkylene compound oralkylpolyglucoside. The common catalysts are those containing stablenitroxide radicals where geometrical, chemical or sterical factorsprevent the formation of a nitrone as depicted below: ##STR19## Thenitroxyl function can be part of a cyclic or acyclic compound, anorganic residue, or a polymeric compound. Among the compounds containingstable nitroxide radicals are the hindered nitroxides which may haveone, two or several nitroxide containing groups. Such compounds belong,but are not limited, to the following classes of nitroxides:

1) cyclic nitroxides containing one nitroxide radical, viz., 2,2,6,6(cis and trans)tetrasubstituted piperidine N-oxyl, e.g.,2,2,6,6-tetramethylpiperidine N-oxyl; 2,2,5,5 (cis and trans)tetrasubstituted pyrrolidine N-oxyl; e.g.,2,2,5,5-tetramethylpyrrolidine N-oxyl; 5,5-dimethyl-2,2-disubstitutedpyrrolidine N-oxyl; and (cis trans) 2,5-dimethyl-2,5-disubstitutedpyrrolidine-N-oxyl. Other cyclic nitroxides containing one nitroxideradical are: a) 2,2,6,6-tetramethylpiperidine N-oxyl compounds whichcontain a further substituent in, but not limited to, the 4-position,e.g., 4-acetamido-2,2,6,6-tetramethylpiperidine N-oxyl;4-phenoxy-2,2,6,6-tetramethylpiperidine N-oxyl; and compounds of theformula ##STR20## where X is 0, N, S, P or C, and Y is a a C-, P-, S-,N- or 0- containing group, or X and Y together are part of an organicresidue or a polymer; and b) 2,2,5,5-tetramethylpyrrolidine N-oxylcompounds which contain a further substituent in, but not limited to,the 3-position, e.g., 3-carbamoyl-2,2,5,5-tetramethylpyrrolidine N-oxyl;3-cyano-2,2,5,5-tetramethylpyrrolidine N-oxyl; and compounds of theformula ##STR21## where X and Y are as defined above. 2) cyclicnitroxides containing two nitroxide radicals, e.g.,bis-4,4'-(2,2,6,6-tetramethylpiperidine N-oxyl) oxamide;bis-3,3'-(2,2,5,5-tetramethylpyrrolidine N-oxyl) oxamide; and compoundsof the formulae ##STR22##

3) cyclic nitroxides containing several nitrooxide radicals, e.g.,compounds of the formulae ##STR23## where n is an integer 5 to 5000,preferably 10 to 2000, more preferably 15 to 500.

4) acyclic nitroxides of the formula ##STR24## where each of R, R₁, R₂,R₃, R₄ and R₅ is other than hydrogen, i.e., an alkyl group, an arylgroup, etc., e.g., di-t-butylamine N-oxyl and the compound having theformula ##STR25##

5) acyclic nitroxides of the formula ##STR26## where X and Y are asdefined above.

It should be understood that although certain of the moietiesrepresented by the group X-Y in the above compounds are unstable in thereaction mixture, the reaction is not adversely affected since themoieties are away from and, therefore, do not involve the catalyticcenter. Other suitable catalysts may be employed in the process of theinstant invention, e.g., those set forth in "Free Nitroxyl Radicals" byE. G. Rozantsev, Plenum Press. New York; London (1970), "OrganicChemistry of Stable Free Radicals" by A. R. Forrester, et al., AcademicPress London and New York (1968), "Spin Labeling in Pharmacology", J. L.Holtzman, Academic Press (1984), and Chemicals Review, Vol. 78(1), pgs.37-64(1978). Moreover, the macrocyclic molecules described in U.S. Pat.No. 4,442,250 and U.S. Pat. No. 4,780,493 can be oxidized to thecorresponding N-oxyl derivatives and utilized as catalysts in theprocess of the instant invention. In addition, it should be madeunderstood that a mixture of hindered nitroxide compounds may beemployed as the catalyst in the process of the instant invention andsuch catalyst mixtures are intended to be included within the scope ofthe instant invention.

The preparation of the carboxylates is conducted at a temperature offrom -10° to 50° C., preferably between -5° and 40° C., more preferablybetween 10° and 30° C.

As to reaction times, the rate of addition of the oxidizing agentdetermines the duration of the reaction. Thus, the addition of theoxidizing agent is at a rate such that the oxidizing agent does notaccumulate in the reaction mixture. Generally, the oxidizing agent isadded over a period of 2 to 3 hours, after which time the reactionmixture is allowed to react for an additional 30 to 60 minutes.Therefore, the total reaction time is at least 3 hours, preferablybetween 3 and 4 hours.

It should be understood that the resultant carboxylates may possessvarying levels of carboxylation depending on the stoichiometry of thereaction. Thus, the ratio [mole of starting material]/[mole ofcarboxylate] can be tuned to a preset level, depending upon the amountof oxidizing agent employed, i.e., the level of carboxylation is afunction of the level of oxidizing agent.

The primary hydroxyl group-containing polyoxyalkylene siloxanes employedin preparing the carboxylates of formula IA are commercially availablefrom Genesee Polymers Corporation and from Petrarch System whereas thecorresponding siloxanes employed in preparing the carboxylates offormula IB are commercially available from Union Carbide. In addition,the primary hydroxyl group-containing polyoxyalkylene amines employed inpreparing the carboxylates of formula IIA are commercially availablefrom BASF; the corresponding amines employed in preparing thecarboxylates of formula IIB are commercially available from SandozChemicals Corp.; and the corresponding amines employed in preparing thecarboxylates of formula IIC are commercially available from AkzoChemicals. Analogously, the corresponding amines employed in preparingthe carboxylates of formulae IID, IIE and IIF, the alkylpolyoxyalkylenealcohols employed in preparing the carboxylates of formula III, thepolyoxyalkylene block polymers employed in preparing the carboxylates offormula IV, the alkylamidepolyoxyalkylenes employed in preparing thecarboxylates of formula V, and the alkyl polyglucosides employed inpreparing the carboxylates of formulae VIA and VIB are either known andobtained by methods described in the literature, or where not known, maybe obtained by methods analogous to those described in the literature.

Although many of the carboxylates prepared by the process of the instantinvention are known, the polyoxyalkylene amine andalkylamidepolyoxyalkylene carboxylates are novel compounds and, as such,they represent another aspect of the instant invention.

The following examples are for the purposes of illustration only and arenot intended in any way to limit the scope of the instant invention.

EXAMPLE 1 Preparation of Polyoxyalkylene Siloxane Carboxylate of FormulaIA (R is Propyl; R' is Methyl; m is 0, n is 4 and p is 27) Process A:(Employing a Liquid Oxidizing Agent)

To a 1000 ml beaker equipped with an overhead stirrer is added 91.35 gof PS-556 (a carbinol terminated polydimethylsiloxane having a molecularweight of 1000 and available commercially from Petrarch System, Bristol,Pa.), 12.5 g of sodium bicarbonate and 1.14 g of Tempo(2,2,6,6-tetramethylpiperidine N-oxyl). To the stirred reaction mixtureis added, portionwise over a period of 3 hours, 385 ml of a 1.91 Maqueous sodium hypochlorite solution (freshly prepared, protectedagainst light by an aluminum foilwrap, and adjusted to a pH of 8-6 bythe addition of sodium bicarbonate). The resultant reaction mixture isstirred for an additional hour and sodium bisulfite is added to get anegative reading in the starch-iodide test. The reaction mixture is thenconcentrated by ultrafiltration to obtain the desired carboxylate insodium salt form.

Process B: (Employing a Solid or Gaseous Oxidizing Agent)

To a 2000 ml beaker equipped with an overhead stirrer is added 500 ml ofdistilled water and 1.14 g of Tempo. With stirring, 91.35 g of PS-556 isdissolved in the aqueous solution and the pH of the resultant solutionis adjusted to 8.6 by the addition of sodium bicarbonate. To the stirredmixture is added, portionwise at 30 minute intervals over a period of 3hours, 156 g of calcium hypochlorite (67.2%), and the pH is adjusted to8.6, if necessary, by the addition of sodium bicarbonate every time aportion of calcium hypochlorite is added. The resultant reaction mixtureis stirred for an additional hour and sodium bisulfite is added to get anegative reading in the starchiodide test. The reaction mixture is thenconcentrated to obtain the desired carboxylate in sodium salt form.

EXAMPLE 2 Preparation of polyoxyalkylene amine carboxylate of formulaIIA (the sum of the m's is ˜16; n is 2; and the sum of the p's is ˜12,calculated by disregarding the ethylene diamine contribution) Process A(Employing a Liquid Oxidizing Agent)

To a 1000 ml beaker equipped with an overhead stirrer is added 103 g ofTetronic-304 (an ethylene diamine based polyoxyalkylene amine having amolecular weight of 1650 and available commercially from BASF), 12.5 gof sodium bicarbonate and 1.56 g of Tempo. To the stirred reactionmixture is added, portionwise over a period of 3 hours, 525 ml of a 1.91M aqueous sodium hypochlorite solution (freshly prepared, protectedagainst light by an aluminum foil wrap and adjusted to a pH of 8.6 bythe addition of sodium bicarbonate). The resultant reaction mixture isstirred for an additional hour and acidified to a pH of between 2 and 3with hydrochloric acid. The acidic reaction mixture is then heated tothe cloud point and the organic upper layer is separated from theaqueous phase to obtain the desired carboxylate as an oily liquid.

Process B (Employing a Solid or Gaseous Oxidizing Agent)

To a 2000 ml beaker equipped with an overhead stirrer is added 500 ml ofdistilled water and 1.56 g of Tempo. With stirring, 103 g ofTetronic-304 is dissolved in the aqueous solution and the pH of theresultant solution is adjusted to 8.6 by the addition of sodiumbicarbonate. To the stirred mixture is added, portionwise at 30 minuteintervals over a period of 3 hours, 213 g of calcium hypochlorite(67.2%), and the pH is adjusted to 8.6, if necessary, by the addition ofsodium bicarbonate every time a portion of calcium hypochlorite isadded. The resultant reaction mixture is stirred for an additional hourand acidified to a pH of between 2 and 3 with hydrochloric acid. Theacidic reaction mixture is then heated to the cloud point and theorganic upper layer is separated from the aqueous phase to obtain thedesired carboxylate as an oily liquid.

EXAMPLE 3 Preparation of polyoxyalkylene amine carboxylate of formulaIIC (m is 0; the sum of the p's is 13 and x is an average value ofbetween 10 and 12) Process A (Employing a Liquid Oxidizing Agent)

To a 1000 ml beaker equipped with an overhead stirrer is added 100 g ofEthomeen C/25 (a fatty amine based polyoxyalkylene amine having amolecular weight of 860 and available commercially from Akzo Chemicals,Inc.), 12.5 g of sodium bicarbonate and 1.45 g of Tempo. To the stirredreaction mixture is added, portionwise over a period of 3 hours, 490 mlof a 1.91 M aqueous sodium hypochlorite solution (freshly prepared,protected against light by an aluminum foil wrap and adjusted to a pH of8.6 by the addition of sodium bicarbonate). The resultant reactionmixture is stirred for an additional hour and acidified to a pH ofbetween 2 and 3 with hydrochloric acid. The acidic reaction mixture isthen heated to the cloud point and the organic upper layer is separatedfrom the aqueous phase to obtain the desired carboxylate as an oilyliquid.

Process B (Employing a Solid or Gaseous Oxidizing Agent)

To a 2000 ml beaker equipped with an overhead stirrer is added 500 ml ofdistilled water and 1.45 g of Tempo. With stirring, 100 g of EthomeenC/25 is dissolved in the aqueous solution and the pH of the resultantsolution adjusted to 8.6 by the addition of sodium bicarbonate. To thestirred mixture is added, portionwise at 30 minute intervals over aperiod of 3 hours, 198 g of calcium hypochlorite (67.2%) and the pH isadjusted to 8.6, if necessary, by the addition of sodium bicarbonateevery time a portion of calcium hypochlorite is added. The resultantreaction mixture is stirred for an additional hour and acidified to a pHof between 2 and 3 with hydrochloric acid. The acidic reaction mixtureis then heated to the cloud point and the organic upper layer isseparated from the aqueous phase to obtain the desired carboxylate as anoily liquid.

EXAMPLE 4 Preparation of Polyoxyalkylene Amine Carboxylate of FormulaIIF (R is methyl; m is 0; the sum of the p's is 13; x is 12 to 14; andX.sup.⊖ is chloride): Process A (Employing a Liquid Oxidizing Agent)

To a 1000 ml beaker equipped with an overhead stirrer is added 100 g ofEthoquad C/25 (a dialkylamine based polyoxyalkylene quaternary aminehaving a molecular weight of 925 and available commercially from AkzoChemicals, Inc.), 30 g of sodium bicarbonate and 1.35 g of Tempo. To thestirred reaction mixture is added, portionwise over a period of 3 hours,455 ml of a 1.91 M aqueous sodium hypochlorite solution (freshlyprepared, protected against light by an aluminum foil wrap and adjustedto a pH of 8.6 by the addition of sodium bicarbonate). The resultantreaction mixture is stirred for an additional hour and concentrated bynanofiltration. The resultant viscous liquid is then acidified to a pHof between 2 and 3 with hydrochloric acid to obtain the desiredcarboxylate.

Process B (Employing a Solid or Gaseous Oxidizing Agent)

To a 2000 ml beaker equipped with an overhead stirrer is added 500 ml ofdistilled water and 1.35 g of Tempo. With stirring, 100 g of EthoquadC/25 is dissolved in the aqueous solution and the pH of the resultantsolution is adjusted to 8.6 by the addition of sodium bicarbonate. Tothe stirred mixture is added, portionwise at 30 minute intervals over aperiod of 3 hours, 185 g of calcium hypochlorite (67.2%) and the pH isadjusted to 8.6, if necessary, by the addition of sodium bicarbonateevery time a portion of calcium hypochlorite is added. The resultantreaction mixture is stirred for an additional hour and concentrated bynanofiltration. The resultant viscous liquid is then acidified to a pHof between 2 and 3 with hydrochloric acid to obtain the desiredcarboxylate.

EXAMPLE 5 Preparation of Alkylpolyoxyalkylene Carboxylate of Formula III(R is the residue of a mixture of C₁₀ -C₁₄ straight chain alcohols; m is0 and n is 6) Process A (Employing a Liquid Oxidizing Agent and a CyclicNitroxide Containing Two Nitroxide Radicals as Catalyst) a) Preparationof bis-4,4'-(2,2,6,6-tetrametylpiperidine) oxamide

To a three-neck flasksequipped with a thermometer, a mechanical stirrer,a condenser and a dropping funnel is added 300 ml of ethanol, 300 ml oftoluene, 150 g (1 mole) of 4-amino-2,2,6,6-tetramethylpiperidine and 73g (0.5 moles) of diethyloxalate. The resultant mixture is then refluxedfor 10 hours and cooled to room temperature. The resultant white solidis then collected by filtration and dried in vacuo to obtain the desiredcompound.

b) Preparation of bis-4,4'-(2,2,6,6-tetramethylpiperidine N-oxyl)oxamide

In accordance with a modification of the procedure set forth by M. G.Rosen, et al. in Synthetic Communications, Vol. 5 (6), pgs. 409-413(1975), the compound prepared in a) above, was oxidized as follows:

To a three-neck flask equipped with an overhead stirrer is added 36.6 g(0.1 moles) of the compound prepared in a) above, 250 ml of methanol,100 ml of acetonitrile, 14 g of sodium bicarbonate and 5 g (0.015 moles)of sodium tungstate dihydrate. After cooling the resultant mixture on anice bath, 250 ml of hydrogen peroxide (30% soln.) was added to themixture and, after removing the ice bath, the reaction mixture wasstirred at room temperature for 3 days. The reaction mixture was thenagain cooled on an ice bath, an additional 250 ml of hydrogen peroxide(30% soln.) was added to the mixture and, after removing the ice bath,the reaction mixture was stirred at room temperature for 5 days. Thereaction mixture was then transferred to a beaker containing 600 g ofcrushed ice, after which time the resultant mixture was triturated andallowed to warm to room temperature. After filtration, the resultantcrystals were dried overnight at 80° C. to obtain the desired compound.

Preparation of the Title Compound

To a 1000 ml beaker equipped with an overhead stirrer is added 127.5 gof Tergitol 24L-60N (an alkylpolyoxyalkylene alcohol having a molecularweight of 510 and available commercially from Union Carbide), 750 ml ofwater, 31 g of sodium bicarbonate and 20 g of the compound prepared inb) above. To the stirred reaction mixture is added, portionwise over aperiod of 3 hours, 525 ml of a 1.91 M aqueous sodium hypochloritesolution (freshly prepared, protected against light by an aluminum foilwrap and adjusted to a pH of 8.6 by the addition of sodium bicarbonate).The resultant reaction mixture is stirred for an additional hour andfiltered to recover the catalyst which can be reused withoutreactivation. The resultant filtrate is then acidified to a pH ofbetween 2 and 3 with hydrochloric acid. The acidic reaction mixture isthen heated to the cloud point and the organic upper layer is separatedfrom the aqueous phase to obtain the desired carboxylate as an oilyliquid.

Process B (Employing a Gaseous Oxidizing Agent)

A 1000 ml reactor is equipped with an overhead stirrer, a thermometer, apH electrode, and a chlorine-disperser for subsurface addition. The pHelectrode is connected to an ACUMET pH-meter for monitoringautomatically the pH and adjusting it to a pre-set value of 8.6 byadding a 50% solution of sodium hydroxide. To the reactor is added 600ml of distilled water, 3.14 g of Tempo and 22 g of sodium bicarbonate.With stirring, 255 g of Tergitol 24L-60N is dissolved in the aqueoussolution and the pH of the resultant solution is adjusted to 8.6 by theaddition of sodium bicarbonate. A slow but continuous stream of chlorineis then bubbled into the stirred reaction mixture over a period of 3hours, while the temperature is maintained at 25° C. The flow ofchlorine is then stopped and the resultant reaction mixture is stirredfor an additional hour. The ACUMET automatic dispenser is thendisconnected while a flow of chlorine is bubbled into the rectionmixture to lower the pH to 2. The acidic reaction mixture is then heatedto its cloud point and the organic upper layer is separated from theaqueous phase to obtain the desired carboxylate as a colorless toslightly brown oily liquid.

EXAMPLE 6 Preparation of Polyoxyalkylene Block Polymer Carboxylate offormula IV (m+p is ˜8, and n is ˜22 ) Process A (Employing a LiquidOxidizing Agent and a Cyclic Nitroxide Containing Several NitroxideRadicals as Catalyst) a) Preparation ofPolyvinylbenzyl-4-0-2,2,6,6-tetramethylpiperidine N-oxyl

To a flame-dried, three-neck flask equipped with a nitrogen inlet-outletand a magnetic stirring bar is added 5 g of4-hydroxy-2,2,6,6-tetramethylpiperidine N-oxyl and 200 ml of anhydrousdimethylformanide. To the mixture is added, portionwise and under a flowof nitrogen, 2 g of sodium hydride and the resultant mixture is stirredat room temperature for 45 minutes. 10 g of polyvinylbenzyl chloride isthen added, portionwise, and the resultant mixture is stirred at roomtemperature for 10 hours. The reaction mixture is then drowned in 1liter of icy-cold water and the resultant pink precipitate is isolatedby filtration and dried in vacuo overnight to obtain the desiredcompound.

Preparation of the Title Compound

To a 1000 ml beaker equipped with an overhead stirrer is added 120 g ofPluronic L-42 (a polyoxyalkylenepolyoxyalkylene block polymer having amolecular weight of 1630 and available commercially from BASF), 12.5 gof sodium bicarbonate and 10 g of the compound prepared in a) above. Tothe stirred reaction mixture is added, portionwise over a period of 3hours, 310 ml of a 1.91 M aqueous sodium hypochlorite solution (freshlyprepared, protected against light by an aluminum foil wrap and adjustedto a pH of 8.6 by the addition of sodium bicarbonate). The resultantreaction mixture is stirred for an additional hour and filtered torecover the catalyst which can be reused without reactivation. Theresultant filtrate is then acicified to a pH of between 2 and 3 withhydrochloric acid. The acidic reaction mixture is then heated to thecloud point and the organic upper layer is separated from the aqueousphase to obtain the desired carboxylate as an oily liquid.

Process B (Employing a Solid or Gaseous Oxidizing Agent)

To a 2000 ml beaker equipped with an overhead stirrer is added 500 ml ofdistilled water and 0.92 mg of Tempo. With stirring, 120 g of PluronicL-42 is dissolved in the aqueous solution and the pH of the resultantsolution is adjusted to 8.6 by the addition of sodium bicarbonate. Tothe stirred mixture is added, portionwise at 30 minute intervals over aperiod of 3 hours, 125.33 g of calcium hypochlorite (67.2%) and the pHis adjusted to 8.6, if necessary, by the addition of sodium bicarbonateevery time a portion of calcium hypochlorite is added. The resultantreaction mixture is stirred for an additional hour and acidified to a pHof between 2 and 3 with hydrochloric acid. The acidic reaction mixtureis then heated to the cloud point and the organic upper layer isseparated from the aqueous phase to obtain the desired carboxylate as anoily liquid.

EXAMPLE 7 Preparation of Alkylamidepolyoxyalkylene Carboxylate ofFormula V (R is the Residue of a Mixture of C₁₀ -C₁₂ straight ChainAlcohols; R₁ is a moiety (C₂ H₄ O)_(n-1) CH₂ -Coo.sup.⊖ X.sup.⊕ ; m is Oand the Sum of the n's is 7 ) Process A (Employing a Liquid OxidizingAgent)

To a 1000 ml beaker equipped with an overhead stirrer is added 100 g ofAlkamidox C-5 (an alkylamidepolyoxyalkylene having a molecular weight of521 and available commercially from Alkaril Chemical), 12.5 g of sodiumbicarbonate and 2.4 g of Tempo. To the stirred reaction mixture isadded, portionwise over a period of 3 hours, 804 ml of a 1.91 M aqueoussodium hypochlorite solution (freshly prepared, protected against lightby an aluminum foil wrap and adjusted to a pH of 8.6 by the addition ofsodium bicarbonate). The resultant reaction mixture is stirred for anadditional hour and acidified to a pH of between 2 and 3 withhydrochloric acid. The acidic reaction mixture is then heated to thecloud point and the organic upper layer is separated from the aqueousphase to obtain the desired carboxylate as on oily liquid.

Process B (Employing a Solid or Gaseous Oxidizing Agent)

To a 2000 ml beaker equipped with an overhead stirrer is added 500 ml ofdistilled water and 2.4 g of Tempo. With stirring, 100 g of AlkamidoxC-5 is dissolved in the aqueous solution and the pH of the resultantsolution is adjusted to 8.6 by the addition of sodium bicarbonate. Tothe stirred mixture is added, portionwise at 30 minute intervals over aperiod of 3 hours, 327 g of calcium hypochlorite (67.2%) and the pH isadjusted to 8.6, if necessary, by the addition of sodium bicarbonateevery time a portion of calcium hypochlorite is added. The resultantreaction mixture is stirred for an additional hour and acidified to a pHof between 2 and 3 with hydrochloric acid. The acidic reaction mixtureis then heated to the cloud point and the organic upper layer isseparated from the aqueous phase to obtain the desired carboxylate as anoily liquid.

EXAMPLE 8 Preparation of Alkylpolyglucoside Carboxylate of Formula VIB Ris C₁₀ -C₁₃ and x is 0.6) Process A (Employing a Liquid Oxidizing Agent)

To a 1000 ml beaker equipped with an overhead stirrer is added 100 g ofAPG-625 (an alkylpolyglucoside having a molecular weight of 429 andavailable commercially from Henkel Corporation as a 50% dispersion inwater), 30 g of sodium bicarbonate and 1.46 g of Tempo. To the stirredreaction mixture is added, portionwise over a period of 3 hours, 490 mlof a 1.91 M aqueous sodium hypochlorite solution (freshly prepared,protected against light by an aluminum foil wrap and adjusted to a pH of8.6 by the addition of sodium bicarbonate). The resultant reactionmixture is stirred for an additional hour, after which time it isconcentrated by nanofiltration to obtain the desired carboxylate as aviscous liquid.

Process B (Employing a Solid or Gaseous Oxidizing Agent)

To a 2000 ml beaker equipped with an overhead stirrer is added 500 ml ofdistilled water and 1.46 g of Tempo. With stirring, 200 g of APG-625 isdissolved in the aqueous solution and the pH of the resultant solutionis adjusted to 8.6 by the addition of sodium bicarbonate. To the stirredmixture is added, portionwise at 30 minute intervals over a period of 3hours, 200 g of calcium hypochlorite (67.2%) and the pH is adjusted to8.6, if necessary, by the addition of sodium bicarbonate every time aportion of calcium hypochlorite is added. The resultant reaction mixtureis stirred for an additional hour after which time it is concentrated bynanofiltration to obtain the desired carboxylate as a viscous liquid.

What is claimed is:
 1. A polyoxyalkylene amine carboxylate selected fromthe group consisting of:a) a compound of formula IIA: ##STR27## whereeach m is an integer 1 to 25;n is an integer 2 to 4; and each p is aninteger 1 to 60; b) a compound of formula IIB: ##STR28## where each m is0 or an integer 1 to 30;n is 0 or an integer 1 to 10; each p is aninteger 3 to 30; and x is an integer 5 to 24; c) a compound of formulaIID: ##STR29## where each m is 0 or an integer 1 to 20; each p is aninteger to 3 to 40; and x is an integer 6 to 20; d) a compound offormula IIE: ##STR30## where each m is 0 or an integer 1 to 40; each pis an integer 3 to 20; x is an integer 6 to 20; and X.sup.⊖ is an anion;and e) a compound of formula IIF: ##STR31## where R is methyl, ethyl, orbenzyl; each m is 0 or an integer 1 to 40; each p is an integer 3 to 20;x is an integer 6 to 20; and X.sup.⊖ is an anion.
 2. A polyoxyalkyleneamine carboxylate according to claim 1 of formula IIA: ##STR32## whereeach m, n and p are as defined in claim
 1. 3. A polyoxyalkylene aminecarboxylate according to claim 1 of formula IIB: ##STR33## where each m,n, each p and x is as defined in claim
 1. 4. A polyoxyalkylene aminecarboxylate according to claim 1 of formula IID: ##STR34## where each m,each p and x is as defined in claim
 1. 5. A polyoxyalkylene aminecarboxylate according to claim 1 of formula IIE: ##STR35## where each m,each p, x and X.sup.⊖ is as defined in claim
 1. 6. A polyoxyalkyleneamine carboxylate according to claim 1 of formula IIF: ##STR36## whereR, each m, each p, x and X.sup.⊖ is as defined in claim 1.